Allyl esters of mono-substituted dithiocarbamic acids



United States Pa n ALLYL ES'IERS 'OF MONO-SUBSTITUTED DITHIOCARBAMIC ACIDS Marion W. Harman, Nitro, and Harry W. Kilbourne,

' (dodecylbenzene sodium sulfonate).

South Charleston, W. Va., assignors to Monsantov Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application November 10, 1955 Serial No. 546,275

6 Claims. (Cl. 260-455) This invention relates to a new class of compounds and to methods for their preparation. More particularly, this invention relates to allyl esters of dithiocarbamic acids containing one hydrogen on the nitrogen.

The compounds of this invention may be represented by the general formula Example 1 In a reactor provided with a sealed stirrer, thermometer, reflux condenser, dropping funnel and ice-bath was charged 59.1 grams (1 mole) of isopropylamine, 160 grams (1 mole) of 25% sodium hydroxide and 300 grams of water. To this mix was added with stirring over a period of 7 minutes at 1522 C. 76 grams (1 mole) of carbon disulfide. The ice-bath was then removed and stirring continued for 30 minutes. Thereupon 76.5 grams (l'mole) of allyl chloride was added in one portion, causing the temperature to rise from 25 to 52 C. in 12 minutes. Stirring was then continued for 4 hours and the product which separated was washed neutral with water, filtered through clay and heated in vacuo up to 100 C./1 mm. The allyl isopropyldithiocarbamate so obtained was an amber oil. The yield was 83.3% of the theoretical. Analysis gave 8.04% nitrogen and 34.87% sulfur as compared to 7.99% nitrogen and 36.58% sulfur calculated for C7H13NS2- Example 2 In the procedure of Example 1, 124 grams (1 mole) of 25% methylarnine was substituted for the isopropylamine. The exothermic reaction caused the temperature to rise from 23 to 49 C. in 16 minutes. The reaction mixture was stirred for hours and the product isolated as described. The allyl methyldithiocarbamate was an amber oil analyzing 10.0% nitrogen and 40.53% sulfur as compared to 9.51% nitrogen and 43.55% sulfur calculated for C H NS The yield was 76.6% of the theoretical.

Example 3 In a reactor as described in Example 1 there was charged 62.6 grams (0.5 mole) of 2,5-endomethylene 2,895,980 Patented July 21, 1959 cyclohexylmethylamine, 80 grams (0.5 mole) of 25% sodium hydroxide and 350 grams of water containing 0.5 gram of a 30% solution of a surface active agent To this solution Was added in minutes at -25 C. 38 grams (0.5 mole) of carbon disulfide. The ice-bath was removed, stirring continued for 3 hours and then 38.3 grams (0.5

mole) of allyl chloride added in one portion, causing'a temperature rise from 24 to 39 C. in 10 minutes. After stirring for an additional 5 hours, the product was taken up in ether, washed neutral with water and the solvent removed in vacuo. The allyl N-2,5-endomethylene cyclohexyl methyldithiocarbamate, an amber oil, was obtained in 89.6% theory yield. Analysis gave 6.24% nitrogen and 23.21% sulfur as compared to 5.80% nitrogen and 26.56% sulfur calculated for C H NS Example 4 carbamate was a red oil obtained in 85.7% theory yield.

Analysis gave 7.16% nitrogen and 30.65% sulfur as compared to 6.89% nitrogen and 31.54% sulfur calculated for C8H13NOSZ.

In a similar manner and substituting the appropriate reactants, other examples were prepared. The amber liquids obtained had the following analyses:

Example 8 In a reactor as described was charged 31.3 grams (0.5 mole) of 72% ethylamine, grams (0.5 mole) of 25% sodium hydroxide and 150 grams of water. To this solution was added in 5 minutes at 1520 C. 38 grams (0.5 mole) of carbon disulfide. After stirring for 45 minutes with ice-bath removed, a clear solution was obtained. Then, 38.3 grams (0.5 mole) of allyl chloride was added in one portion, causing the temperature to rise from 27 to 50 C. in 10 minutes. The product was stirred for 5 hours, washed neutral with water and dried in vacuo at C./ 12 mm. The allyl N-ethyldithiocarbamate, a red oil, was obtained in 80.6% theory yield. Analysis gave 8.77% nitrogen and 38.22% sulfur compared to 8.68% nitrogen and 39.76% sulfur calculated for CGHHNSZ. i

3 By a similar procedure, the following new compounds were prepared. Example 9 was an amber liquid while the other examples comprise red liquids:

' 4 3. A compound of the structure It is intended to cover all changes and modifications of the examples of the invention herein chosen for purposes of disclosure which do not constitute departures 25 from the spirit and scope of the invention.

What is claimed is: 1. A compound of the structure H RN- @s-a11 1 30 where R represents an organic radical selected from the group consisting of alkyl, alkenyl, aralkyl and alicyclic radicals.

2. A compound of the structure 35 H II RNC-Selly1 where R is an alkyl group of less than three carbon 40 atoms.

where R is an alkenyl group.

4. The compound of the structure CH NHCSSCH CH=CH 5. The compound of the structure C H NHCSSCH CH=CH 6. The compound of the structure CH =CHCH NHCSSCH CH=CH References Cited in the file of this patent UNITED STATES PATENTS 2,127,375 Bousquet Aug. 16, 1938 2,579,384 Handy et a1. Dec. 18, 1951 2,786,866 Hook et a1. Mar. 26, 1957 

1. A COMPOUND OF THE STRUCTURE 